JP6362029B2 - Nickel sulfide raw material processing method - Google Patents

Nickel sulfide raw material processing method Download PDF

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JP6362029B2
JP6362029B2 JP2014172099A JP2014172099A JP6362029B2 JP 6362029 B2 JP6362029 B2 JP 6362029B2 JP 2014172099 A JP2014172099 A JP 2014172099A JP 2014172099 A JP2014172099 A JP 2014172099A JP 6362029 B2 JP6362029 B2 JP 6362029B2
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chlorine
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sulfide
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松本 伸弘
伸弘 松本
徹 北崎
徹 北崎
貴雄 大石
貴雄 大石
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Sumitomo Metal Mining Co Ltd
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Description

本発明は、ニッケルを含む複数種の金属硫化物を原料としてニッケルを製造する、塩素浸出工程を含んだニッケルの湿式製錬プロセスにおいて、原料処理比率を調整するために、原料処理比率に応じて塩素浸出液の銅濃度を適正値に調整する、ニッケル硫化物原料の処理方法に関するものである。   The present invention produces nickel from a plurality of metal sulfides containing nickel as a raw material. In a nickel hydrometallurgy process including a chlorine leaching process, the raw material treatment ratio is adjusted in order to adjust the raw material treatment ratio. The present invention relates to a nickel sulfide raw material processing method for adjusting the copper concentration of a chlorine leaching solution to an appropriate value.

ニッケルおよびコバルトの製錬においては、例えば、ニッケル硫化鉱石を溶鉱炉で溶解して得られるニッケル硫化物や、ニッケル酸化鉱石に硫黄を添加して電気炉で溶解して得られるニッケル硫化物等、いわゆる乾式製錬法で得られたNi等のニッケル硫化物を主成分とするニッケルマットが生産されている。 In the smelting of nickel and cobalt, for example, nickel sulfide obtained by melting nickel sulfide ore in a blast furnace, nickel sulfide obtained by melting sulfur in nickel oxide ore and melting in an electric furnace, so-called Nickel mats mainly composed of nickel sulfide such as Ni 3 S 2 obtained by a dry smelting method are produced.

一方で、低ニッケル品位のニッケル酸化鉱石を加圧酸浸出(High Pressure Acid Leaching、通称HPAL)して、その加圧酸浸出液から鉄をはじめとする不純物を除去した後、湿式硫化反応によって、例えば硫化水素ガスをニッケルイオンおよびコバルトイオンを含んだ浸出液中に吹込むことによって、得られたNiS等の硫化物を主成分とするニッケルおよびコバルトを含む混合硫化物(以降、混合硫化物と称する。)も生産されている。   On the other hand, after low-grade nickel oxide ore is subjected to pressure acid leaching (High Pressure Acid Leaching, commonly called HPAL) and impurities such as iron are removed from the pressure acid leaching solution, wet sulfidation reaction, for example, By mixing hydrogen sulfide gas into a leachate containing nickel ions and cobalt ions, the resulting mixed sulfide containing nickel and cobalt whose main components are sulfides such as NiS (hereinafter referred to as mixed sulfide). ) Is also produced.

上記ニッケルマットや混合硫化物を原料としてニッケル及びコバルトを精製する方法としては、例えば特許文献1に記載されているように、塩素ガスの酸化作用を利用してニッケルマットや混合硫化物を浸出し、浸出されたニッケルイオン及びコバルトイオンを電解採取によって電気ニッケル及び電気コバルトとして製品化する塩素浸出プロセスが実用化されている。   As a method of refining nickel and cobalt using the nickel mat or mixed sulfide as a raw material, for example, as described in Patent Document 1, the nickel mat or mixed sulfide is leached using the oxidizing action of chlorine gas. A chlorine leaching process for commercializing leached nickel ions and cobalt ions as electrolytic nickel and cobalt by electrowinning has been put into practical use.

この方法は、混合硫化物と下記セメンテーション残渣を塩化物水溶液にレパルプした後、そのスラリーに塩素ガスを吹込むことによりニッケル及びコバルトを塩化物水溶液中に塩素浸出する。   In this method, the mixed sulfide and the following cementation residue are repulped into an aqueous chloride solution, and then nickel and cobalt are leached into the aqueous chloride solution by blowing chlorine gas into the slurry.

そこで得られた酸化剤としての2価の銅クロロ錯イオンを含んだ塩素浸出液に、粉砕したニッケルマットを接触させて銅とニッケルの置換反応を行うことにより、ニッケルマット中のニッケルが液に置換浸出され、銅イオンはCuSまたはCu(金属銅)の形態となって固体(セメンテーション残渣の一部)となる。 The resulting nickel leaching solution containing divalent copper chloro complex ions as the oxidant is brought into contact with the crushed nickel mat to perform a substitution reaction between copper and nickel, thereby replacing the nickel in the nickel mat with the solution. The copper ions are leached and become solid (part of cementation residue) in the form of Cu 2 S or Cu 0 (metallic copper).

その置換浸出終液と、ニッケルマットの置換浸出残渣と前記CuSまたはCu(金属銅)の形態となって沈澱した固体とからなるセメンテーション残渣は、固液分離された後、置換浸出終液は次の浄液工程へ、固体のセメンテーション残渣は塩素浸出工程へ送られる。
この浄液工程では、得られた置換浸出終液から鉄、鉛、銅、亜鉛等の不純物を除去すると共に、置換浸出終液中のコバルトを溶媒抽出等の方法を用いて分離する。
次いでニッケルを電解採取して電気ニッケルを製造する方法である。
The cementation residue composed of the substitution leaching final solution, the nickel mat substitution leaching residue, and the solid precipitated in the form of Cu 2 S or Cu 0 (metal copper) is solid-liquid separated, and then the substitution leaching. The final liquid is sent to the next purification process, and the solid cementation residue is sent to the chlorine leaching process.
In this liquid purification step, impurities such as iron, lead, copper, and zinc are removed from the obtained substitution leaching final solution, and cobalt in the substitution leaching final solution is separated using a method such as solvent extraction.
Next, nickel is electrolytically collected to produce electric nickel.

なお、上記塩素浸出プロセスでは、塩素浸出工程で浸出されなかった硫黄を主成分とする塩素浸出残渣は硫黄の回収工程にて処理され、製品硫黄および残渣類として払出される。
この方法はシンプルで、電解採取で発生した塩素ガスを浸出に再利用する等、効率的かつ経済的な生産を実現している。
In the chlorine leaching process, a chlorine leaching residue mainly composed of sulfur that has not been leached in the chlorine leaching step is treated in a sulfur recovery step and discharged as product sulfur and residues.
This method is simple and realizes efficient and economical production such as reusing chlorine gas generated by electrowinning for leaching.

特許文献1に記載されている塩素浸出工程におけるニッケルを含む金属硫化物の塩素浸出反応は、浸出液中の銅イオンの酸化還元反応を利用して金属成分を浸出する反応である。   The chlorine leaching reaction of a metal sulfide containing nickel in the chlorine leaching process described in Patent Document 1 is a reaction in which a metal component is leached using a redox reaction of copper ions in the leaching solution.

前記塩素浸出工程では、2価の銅のクロロ錯イオンが混合硫化物やセメンテーション残渣中の金属を溶解するための直接的な浸出剤として作用し、塩素ガスは銅の1価イオンを2価イオンに酸化することにより間接的に浸出反応に関与する。
そこで、この浸出反応が効率的に進行するためには、塩素浸出液中の銅濃度が10g/L以上であることが条件であり、その銅濃度が高いほど塩素吸収効率が高くなるため、金属成分の浸出率が向上する。
In the chlorine leaching process, divalent copper chloro complex ions act as a direct leaching agent for dissolving mixed sulfides and metals in cementation residues, and chlorine gas divalently converts copper monovalent ions into divalent ions. It is indirectly involved in the leaching reaction by oxidation to ions.
Therefore, in order for this leaching reaction to proceed efficiently, it is a condition that the copper concentration in the chlorine leaching solution is 10 g / L or more, and the higher the copper concentration, the higher the chlorine absorption efficiency. The leaching rate is improved.

一方で、前記置換浸出工程では、塩素浸出液とニッケルマットを接触させることにより、塩素浸出液中の銅イオンとニッケルマット中のニッケルのセメンテーション反応が行われる。
このセメンテーション反応は、固体のニッケルが溶出してニッケルイオンとなり、その溶出したニッケルと電気化学的に当量の液中の銅イオンが固体となるため、置換浸出工程は塩素浸出液中に含まれる銅を固体として除去する脱銅工程であるとも言える。
On the other hand, in the substitution leaching step, a cementation reaction of copper ions in the chlorine leaching solution and nickel in the nickel mat is performed by bringing the chlorine leaching solution into contact with the nickel mat.
In this cementation reaction, solid nickel elutes into nickel ions, and copper ions in the liquid that is electrochemically equivalent to the eluted nickel become solids, so the substitution leaching step is the copper contained in the chlorine leachate. It can also be said that this is a copper removal step of removing as solid.

この塩素浸出液中の銅イオンは、塩素浸出液からセメンテーション残渣として分離されるため、置換浸出終液の銅濃度は0.02g/L以下であり、その後の浄液工程では残った微量の銅を除去すれば良い。また、原料からのインプット見合いの銅は、塩素浸出液の一部を銅電解採取に付することによって銅粉として系外に抜出される。   Since the copper ions in the chlorine leachate are separated from the chlorine leachate as cementation residues, the copper concentration of the substitution leachate is 0.02 g / L or less. Remove it. Moreover, copper corresponding to the input from the raw material is extracted out of the system as copper powder by subjecting a portion of the chlorine leaching solution to copper electrowinning.

上記の通り、塩素浸出プロセスは、原料に含まれる不純物としての銅を上手く利用することで成立している。
すなわち、ニッケルマットや混合硫化物等の原料中に微量に含まれる銅は、ニッケルおよびコバルトを精製する上での不純物ではあるが、前記塩素浸出工程や置換浸出工程では酸化剤として利用され、塩素浸出工程と置換浸出工程の間を、塩素浸出液とセメンテーション残渣として循環している。
As described above, the chlorine leaching process is established by successfully using copper as an impurity contained in the raw material.
That is, copper contained in a trace amount in raw materials such as nickel mat and mixed sulfide is an impurity in refining nickel and cobalt, but is used as an oxidizing agent in the chlorine leaching process and the substitution leaching process, and chlorine Between the leaching process and the displacement leaching process, it is circulated as a chlorine leaching solution and a cementation residue.

図1は、上記塩素浸出プロセスの工程図を示すものである。
図1における数字は、電気ニッケルの生産量を100としたときの塩素ガス量、原料中のニッケル量の当量比のイメージを表す。
塩素浸出工程で浸出剤として使用される塩素ガス量および前記塩素浸出工程と置換浸出工程で処理される硫化物原料の処理量については、電気ニッケルの生産量、すなわち最終工程であるところの電解採取工程における通電電流等によって決定される。
FIG. 1 shows a flow chart of the chlorine leaching process.
The numbers in FIG. 1 represent an image of the equivalent ratio of the chlorine gas amount and the nickel amount in the raw material when the production amount of electric nickel is 100.
Regarding the amount of chlorine gas used as a leaching agent in the chlorine leaching step and the amount of sulfide raw material processed in the chlorine leaching step and the substitution leaching step, the production amount of electronickel, that is, the electrowinning as the final step It is determined by the energization current in the process.

電解採取工程では、浄液工程にて置換浸出終液から浄液された塩化ニッケル溶液を電気分解することにより、塩化ニッケル溶液中のニッケルイオンが陰極に析出して電気ニッケルとなり、塩化ニッケル溶液中の塩化物イオンは陽極表面で塩素ガスを生成して回収される。
効率の差はあるが、基本的には陽極表面で発生する塩素ガス量は電気ニッケルと化学的に当量であり、電解採取工程の通電電流と電気的に当量である。
発生した塩素ガスは塩素浸出に再利用され、そして、理論上はその再利用される塩素ガスと化学的に当量のニッケルを含んだ硫化物原料を処理することができる。
In the electrowinning process, the nickel chloride solution purified from the substitution leaching final solution in the liquid purification process is electrolyzed, so that nickel ions in the nickel chloride solution are deposited on the cathode to form electric nickel. The chloride ions are recovered by generating chlorine gas on the anode surface.
Although there is a difference in efficiency, basically, the amount of chlorine gas generated on the anode surface is chemically equivalent to electric nickel, and is electrically equivalent to the energization current in the electrowinning process.
The generated chlorine gas is reused for chlorine leaching, and theoretically, a sulfide raw material containing nickel that is chemically equivalent to the recycled chlorine gas can be processed.

ところで、乾式製錬法で生産されたニッケルマットには、主成分としての亜硫化ニッケル(Ni)の他に20%程度の金属ニッケルが含まれている。
この金属ニッケルは強い還元力を有していることから、置換浸出工程にて塩素浸出液中の銅イオンを硫化第一銅(CuS)または金属銅(Cu)にまで還元して、固体のセメンテーション残渣として沈澱させることができる。
By the way, the nickel mat produced by the dry smelting method contains about 20% of metallic nickel in addition to nickel subsulfide (Ni 3 S 2 ) as a main component.
Since this metallic nickel has a strong reducing power, the copper ions in the chlorine leaching solution are reduced to cuprous sulfide (Cu 2 S) or metallic copper (Cu 0 ) in the substitution leaching step, and solid As a cementation residue.

一方で、湿式硫化反応によって生産された混合硫化物の主成分は、硫化ニッケル(NiS)および硫化コバルト(CoS)である。
この硫化ニッケルおよび硫化コバルトは金属ニッケルのような強い還元力を持たず、塩素浸出液中の2価の銅クロロ錯イオンの一部を1価の銅クロロ錯イオンに還元することはできても、銅イオンを固体の硫化第一銅(CuS)または金属銅(Cu)にまで還元することはできない。
On the other hand, the main components of the mixed sulfide produced by the wet sulfidation reaction are nickel sulfide (NiS) and cobalt sulfide (CoS).
This nickel sulfide and cobalt sulfide do not have a strong reducing power like metallic nickel, and even though a portion of the divalent copper chloro complex ion in the chlorine leachate can be reduced to a monovalent copper chloro complex ion, Copper ions cannot be reduced to solid cuprous sulfide (Cu 2 S) or metallic copper (Cu 0 ).

したがって、塩素浸出プロセスが成立するには、塩素浸出液中の銅イオンを塩素浸出液からセメンテーション残渣として分離するために必要な最低限のニッケルマットが必要となり、固体の硫化第一銅(CuS)または金属銅(Cu)にまで還元する能力を有さない混合硫化物については、直接塩素浸出工程にて処理される。
また、近年、コスト的に有利な原料として混合硫化物の増産が図られており、混合硫化物の増処理が求められている。
Therefore, in order to establish the chlorine leaching process, a minimum nickel mat necessary for separating copper ions in the chlorine leaching solution from the chlorine leaching solution as a cementation residue is required, and solid cuprous sulfide (Cu 2 S) is required. ) Or mixed sulfides that do not have the ability to reduce to metallic copper (Cu 0 ) are processed directly in the chlorine leaching process.
In recent years, production of mixed sulfides has been increased as a cost-effective raw material, and increased treatment of mixed sulfides has been demanded.

そこで、特許文献2に記載されている、混合硫化物の一部を置換浸出工程で処理する技術が開発・実用化されている。特許文献2の概略工程図を図2に示す。
その技術とは、すなわち、酸化剤としての2価の銅クロロ錯イオンを含んだ塩素浸出液に、混合硫化物を接触させることにより、混合硫化物中のニッケルおよびコバルトの一部が置換浸出されると共に、2価の銅クロロ錯イオンの一部が1価の銅クロロ錯イオンに還元されるものである。
Therefore, a technique described in Patent Document 2 for treating a part of the mixed sulfide in the substitution leaching process has been developed and put into practical use. A schematic process diagram of Patent Document 2 is shown in FIG.
That is, a part of nickel and cobalt in the mixed sulfide is replaced and leached by contacting the mixed sulfide with a chlorine leaching solution containing divalent copper chloro complex ions as an oxidizing agent. At the same time, a part of the divalent copper chloro complex ion is reduced to a monovalent copper chloro complex ion.

次いで、その1価および2価の銅クロロ錯イオンを含んだ塩素浸出液に粉砕したニッケルマットを接触させて、銅とニッケルの置換反応を行うことにより、ニッケルマット中のニッケルが液に置換浸出され、液中の銅イオンはCuSまたはCu(金属銅)の形態となって固体(セメンテーション残渣の一部)となる。
しかし、特許文献2に記載の方法によっても、必要なニッケルマット量が確保できない場合には、混合硫化物の処理量を減らして電気ニッケルの生産量を減少させるアクションを取らざるを得ない。最悪の場合には、置換浸出工程での脱銅が不可能となり、電気ニッケルの製造そのものが成り立たなくなってしまう。
Next, by contacting the pulverized nickel mat with a chlorine leaching solution containing monovalent and divalent copper chloro complex ions and performing a substitution reaction between copper and nickel, the nickel in the nickel mat is substituted and leached into the solution. The copper ions in the liquid become a solid (part of cementation residue) in the form of Cu 2 S or Cu 0 (metallic copper).
However, even if the necessary amount of nickel matte cannot be ensured even by the method described in Patent Document 2, it is necessary to take an action to reduce the amount of mixed sulfides to reduce the production amount of electrolytic nickel. In the worst case, copper removal in the substitution leaching process is impossible, and the production of electro nickel itself cannot be realized.

特開2008−240009号公報JP 2008-240009 A 特開2012−026027号公報JP 2012-026027 A

上記状況に鑑み、コスト的に有利な原料として混合硫化物の増産が図られており、その増処理が求められている。
また、塩素浸出プロセスにおいてニッケルマットと混合硫化物を処理する場合、それぞれの原料に含まれる不純物含有率が異なるため、それぞれの原料の処理比率を変更することにより、工程内へ持ち込まれる銅を始めとする不純物量を容易に調整できることも望まれる。
In view of the above situation, production of mixed sulfides has been increased as a cost-effective raw material, and an increase in the processing has been demanded.
Also, when treating nickel matte and mixed sulfides in the chlorine leaching process, the content of impurities contained in each raw material is different, so changing the treatment ratio of each raw material will start the copper brought into the process. It is also desirable that the amount of impurities to be easily adjusted.

しかし、図3の特許文献2に係る塩素浸出プロセスの工程図に示すごとく、塩素浸出液中の銅濃度を必要以上に高く維持すると、置換浸出工程で塩素浸出液中の銅イオンを固体化するためのニッケルマットの処理量は増加するが、塩素浸出工程と置換浸出工程で処理される硫化物原料の処理量については電気ニッケルの生産量によって決定されるため、相対的に混合硫化物の処理量を制限せざるを得ない。つまり不純物負荷調整のために原料の処理比率調整を実施することが困難である。
また、置換浸出工程でセメンテーション残渣量が増加するため、固液分離等のハンドリングに手間を要すことになり、効率的では無い。
However, as shown in the process chart of the chlorine leaching process according to Patent Document 2 in FIG. 3, if the copper concentration in the chlorine leaching liquid is maintained higher than necessary, the copper leaching liquid in the substitution leaching process is solidified. Although the amount of nickel matte increases, the amount of sulfide raw material processed in the chlorine leaching process and the displacement leaching process is determined by the amount of nickel produced. I have to limit it. That is, it is difficult to adjust the raw material processing ratio for adjusting the impurity load.
Moreover, since the amount of cementation residue increases in the substitution leaching process, it takes time for handling such as solid-liquid separation, which is not efficient.

そこで、化学組成、化合物組成の異なる複数種のニッケルマットと混合硫化物を塩素浸出プロセスにて処理し、その処理比率を容易に調整できる手段や管理方法を確立することが望まれていた。   Accordingly, it has been desired to establish means and a management method that can easily treat the plurality of types of nickel mats and mixed sulfides having different chemical compositions and compound compositions by the chlorine leaching process and adjust the treatment ratio easily.

本発明は、上記従来技術の問題点に鑑みて考案されたものであり、ニッケルを含む複数種の金属硫化物を原料としてニッケルを製造する、塩素浸出工程を含んだニッケルの湿式製錬プロセスにおいて、ニッケルを含む複数種の金属硫化物の原料処理比率を容易にかつ安定的に調整するニッケル硫化物原料の処理方法を提供することを目的とする。   The present invention has been devised in view of the above-mentioned problems of the prior art, and in a nickel hydrometallurgical process including a chlorine leaching process, in which nickel is produced using a plurality of metal sulfides containing nickel as a raw material. An object of the present invention is to provide a nickel sulfide raw material treatment method that easily and stably adjusts the raw material treatment ratio of a plurality of types of metal sulfides containing nickel.

上記目的を達成するため、本発明者らは、塩素浸出液の銅濃度とニッケルを含む複数種の金属硫化物の原料処理比率について研究を重ねた結果、塩素浸出液の銅濃度の管理基準値を調整することによって、亜硫化ニッケルと金属ニッケルを含むニッケルマットと、硫化ニッケルと硫化コバルトを含む混合硫化物の原料処理比率の調整を容易かつ安定的に行うことができることを見出し、本発明の完成に至った。   In order to achieve the above object, the present inventors conducted research on the copper concentration of the chlorine leachate and the raw material treatment ratio of multiple types of metal sulfides containing nickel, and as a result, adjusted the control standard value of the copper concentration of the chlorine leachate. By doing so, it was found that it is possible to easily and stably adjust the raw material treatment ratio of the nickel matte containing nickel subsulfide and metallic nickel and the mixed sulfide containing nickel sulfide and cobalt sulfide. It came.

すなわち、本発明の第1の発明は、ニッケルを製造する湿式製錬プロセスにおけるニッケル硫化物原料の処理方法で、ニッケルを含む金属硫化物を原料としてニッケルを製造する湿式精錬プロセスであって、ニッケルを含む金属硫化物、又は前記ニッケルを含む金属硫化物と下記セメンテーション残渣を塩素浸出用ニッケル原料として用い、その塩素浸出用ニッケル原料に含まれるニッケル及び不純物を塩化物水溶液中に塩素浸出して塩素浸出液を得る塩素浸出工程、前記塩素浸出工程により得られる塩素浸出液に含まれる銅の濃度を、管理基準値(A)に基づいて前記塩素浸出液中の銅濃度を調整した塩素浸出液を得る銅濃度調整工程、ニッケルを含む金属硫化物に塩素浸出液を接触させることで塩素浸出液中の2価銅イオンによりニッケルを含む金属硫化物中のニッケルを置換浸出すると共にCuS又はCuメタルを生成させて銅が除去された置換浸出終液とCuS又はCuメタルを含むセメンテーション残渣を得る置換浸出工程、置換浸出終液中の不純物を除去して塩化ニッケル溶液を得る浄液工程、塩化ニッケル溶液から電解採取法によって金属ニッケルと塩素ガスを回収する電解工程を含むニッケル硫化物原料の処理方法において、下記(1)から(3)に示す手順に従って、前記塩素浸出液中の銅濃度の管理基準値(A)を低下させることによって、亜硫化ニッケルと金属ニッケルを含むニッケルマットの処理量(B)と、硫化ニッケルと硫化コバルトを含む混合硫化物の処理量(C)との合計原料処理量(B+C)に対する、硫化ニッケルと硫化コバルトを含む混合硫化物処理量(C)の処理比率(D=C÷(B+C)×100%)を上昇させることを特徴とするニッケル硫化物原料の処理方法である。
(記)
(1)前記ニッケルマットの処理量(B)から許容可能な塩素浸出液中の銅負荷(A1)および塩素浸出液中の銅濃度の上限値(A2)を決定し、
(2)塩素浸出液中の銅濃度の上限値(A2)に対する混合硫化物処理量の処理比率(D)との関係式(D=f(A2))を導き出す。
(3)前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))と、前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))をD軸に沿って−10移動した式(D+10=f(A2+5))と、式A2=15と、式A2=55に囲まれた範囲にある混合硫化物処理量の処理比率(D)に対応した塩素浸出液中の銅濃度の管理基準値(A)を設定する。
That is, the first invention of the present invention is a nickel sulfide raw material treatment method in a hydrometallurgical process for producing nickel, and is a wet refining process for producing nickel using a metal sulfide containing nickel as a raw material. Or the following cementation residue is used as a nickel raw material for chlorine leaching, and the nickel and impurities contained in the nickel raw material for chlorine leaching are leached into an aqueous chloride solution. Chlorine leaching step for obtaining a chlorine leaching solution, a copper concentration for obtaining a chlorine leaching solution in which the concentration of copper contained in the chlorine leaching solution obtained by the chlorine leaching step is adjusted based on the control standard value (A) adjustment step, the divalent copper ions chlorine in the leaching solution by contacting the chlorine leachate metal sulfide containing nickel nickel Substituted leaching step to obtain a cementation residue containing Cu 2 S or Cu substituted leach final solution by generating copper has been removed metal and Cu 2 S or Cu metal with replacing leaching nickel metal sulphide containing a In the method for treating nickel sulfide raw materials, including a purification step for removing impurities in the substitution leaching final solution to obtain a nickel chloride solution, an electrolysis step for recovering metallic nickel and chlorine gas from the nickel chloride solution by electrowinning, According to the procedure shown in (1) to (3), by reducing the control standard value (A) of the copper concentration in the chlorine leachate, the treatment amount (B) of nickel matte containing nickel subsulfide and metallic nickel, Containing nickel sulfide and cobalt sulfide relative to the total raw material throughput (B + C) with the throughput (C) of the mixed sulfide containing nickel sulfide and cobalt sulfide. A method of processing a nickel sulfide material, characterized in that increasing the treat rate of mixed sulphide throughput (C) (D = C ÷ (B + C) × 100%).
(Record)
(1) Determine the allowable copper load (A1) in the chlorine leachate and the upper limit (A2) of the copper concentration in the chlorine leachate from the nickel mat throughput (B),
(2) A relational expression (D = f (A2)) with the treatment ratio (D) of the mixed sulfide treatment amount with respect to the upper limit (A2) of the copper concentration in the chlorine leachate is derived.
(3) The relational expression (D = f (A2)) is moved by -5 along the A2 axis (D = f (A2 + 5)) and the relational expression (D = f (A2)) is taken as the A2 axis. The equation (D = f (A2 + 5)) moved by -5 along the D axis is surrounded by the equation (D + 10 = f (A2 + 5)) moved by -10 along the D axis, the equation A2 = 15, and the equation A2 = 55. A management reference value (A) for the copper concentration in the chlorine leachate corresponding to the treatment ratio (D) of the mixed sulfide treatment amount in the range is set.

本発明の第2の発明は、ニッケルを含む金属硫化物、又は前記ニッケルを含む金属硫化物と下記セメンテーション残渣を塩素浸出用ニッケル原料として用い、前記塩素浸出用ニッケル原料に含まれるニッケル及び不純物を塩化物水溶液中に塩素浸出して塩素浸出液を得る塩素浸出工程、この塩素浸出工程により得られる塩素浸出液に含まれる銅の濃度を、銅濃度調整工程において前記管理基準値(A)に基づいて調節した塩素浸出液を得る銅濃度調整工程、ニッケルを含む金属硫化物に前記塩素浸出液を接触させることで塩素浸出液中の2価銅イオンにより前記ニッケルを含む金属硫化物中のニッケルを置換浸出すると共にCuA second invention of the present invention uses nickel-containing metal sulfide, or the above-mentioned nickel-containing metal sulfide and the following cementation residue as a nickel raw material for chlorine leaching, and nickel and impurities contained in the nickel raw material for chlorine leaching Chlorine leaching step of leaching chlorine into an aqueous chloride solution to obtain a chlorine leaching solution, and the concentration of copper contained in the chlorine leaching solution obtained by this chlorine leaching step based on the control reference value (A) in the copper concentration adjusting step A copper concentration adjusting step for obtaining an adjusted chlorine leaching solution, by contacting the chlorine leaching solution with a metal sulfide containing nickel, and substituting and leaching nickel in the metal sulfide containing nickel by divalent copper ions in the chlorine leaching solution. Cu 2 S又はCuメタルを生成させて銅が除去された置換浸出終液とCuSubstitute leaching final solution from which copper is removed by forming S or Cu metal and Cu 2 S又はCuメタルを含むセメンテーション残渣を得る置換浸出工程、前記置換浸出終液中の不純物を除去して塩化ニッケル溶液を得る浄液工程、前記塩化ニッケル溶液から電解採取法によって金属ニッケルと塩素ガスを回収する電解工程、を含むニッケルを製造する湿式製錬プロセスにおけるニッケル硫化物原料の処理方法において、Substitution leaching step for obtaining cementation residue containing S or Cu metal, purification step for removing nickel impurities in the substitution leaching final solution to obtain a nickel chloride solution, nickel metal and chlorine gas by electrolytic extraction from the nickel chloride solution In the method for treating nickel sulfide raw material in a hydrometallurgical process for producing nickel, including an electrolysis step of recovering
下記の(1)から(3)の手順に従って、前記塩素浸出液中の銅濃度の管理基準値(A)を低下させることによって、亜硫化ニッケルと金属ニッケルを含むニッケルマットの処理量(B)と、硫化ニッケルと硫化コバルトを含む混合硫化物処理量(C)との合計原料処理量(B+C)に対する、硫化ニッケルと硫化コバルトを含む混合硫化物処理量(C)の処理比率(D=C÷(B+C)×100%)を上昇させることを特徴とするニッケル硫化物原料の処理方法である。According to the following procedures (1) to (3), by reducing the control standard value (A) of the copper concentration in the chlorine leaching solution, the treatment amount (B) of nickel matte containing nickel subsulfide and metallic nickel , The treatment ratio of mixed sulfide treatment amount (C) containing nickel sulfide and cobalt sulfide (D = C ÷ the total raw material treatment amount (B + C) of mixed sulfide treatment amount (C) containing nickel sulfide and cobalt sulfide (B + C) × 100%) is raised, which is a nickel sulfide raw material treatment method.

(記)(Record)
(1).前記ニッケルマットの処理量(B)から許容可能な塩素浸出液中の銅負荷(A1)および塩素浸出液中の銅濃度の上限値(A2)を決定し、(1). Determine the allowable copper load (A1) in the chlorine leachate and the upper limit (A2) of the copper concentration in the chlorine leachate from the nickel mat throughput (B),
(2).塩素浸出液中の銅濃度の上限値(A2)に対する混合硫化物処理量の処理比率(D)との関係式(D=f(A2))を導き出し、(2). A relational expression (D = f (A2)) with the treatment ratio (D) of the mixed sulfide treatment amount with respect to the upper limit value (A2) of the copper concentration in the chlorine leachate is derived,
(3).前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))と、前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))をD軸に沿って−10移動した式(D+10=f(A2+5))と、式A2=15と、式A2=55に囲まれた範囲にある混合硫化物処理量の処理比率(D)に対応した塩素浸出液中の銅濃度の管理基準値(A)を設定する。(3). The relational expression (D = f (A2)) is moved by −5 along the A2 axis (D = f (A2 + 5)) and the relational expression (D = f (A2)) is along the A2 axis− The equation (D = f (A2 + 5)) moved by 5 is moved by −10 along the D axis (D + 10 = f (A2 + 5)), the equation A2 = 15, and the range surrounded by the equation A2 = 55. A control reference value (A) for the copper concentration in the chlorine leachate corresponding to the treatment ratio (D) of the mixed sulfide treatment amount is set.

第2の発明における前記銅濃度調整工程は、前記塩素浸出液の銅濃度が、15〜55g/Lの間で任意に設定された管理基準値から3g/L以上低下した時には、下記(イ)、(ハ)のいずれかの手順を講じ、塩素浸出液の銅濃度が、前記管理基準値から3g/L以上上昇した時には、下記(ロ)の手段を講じ、塩素浸出液の銅濃度が、前記管理基準値から3g/L未満低下した時には、下記(イ)、(ロ)、(ハ)のいずれかの手段を講じ、塩素浸出液の銅濃度が、前記管理基準値から3g/L未満上昇した時には、下記(イ)、(ロ)、(ハ)のいずれかの手段を講じて塩素浸出液中の銅濃度を10g/L以上60g/L以下の範囲に維持することを特徴とする。
(記)
(イ)酸化還元電位が400mV(Ag/AgCl電極基準)以上の塩素浸出液と金属銅を接触させることによって、塩素浸出液中の銅濃度を上昇させる銅補充手段。
(ロ)塩素浸出液を還元して価数が2価の銅イオン濃度を低下させた後に、前記還元後の塩素浸出液を銅電解採取することによって、塩素浸出液中の銅濃度を低下させる脱銅手段。
(ハ)上記(イ)も(ロ)も実施しない中立手段。
In the copper concentration adjusting step according to the second invention, when the copper concentration of the chlorine leaching solution is reduced by 3 g / L or more from a management reference value arbitrarily set between 15 and 55 g / L, the following (A), (C) When the copper concentration of the chlorine leachate is increased by 3 g / L or more from the control standard value, the following measure (b) is taken, and the copper concentration of the chlorine leachate is determined according to the control standard. When the value falls below 3 g / L from the value, the following measures (a), (b), (c) are taken, and when the copper concentration of the chlorine leachate rises below 3 g / L from the control reference value, Any one of the following means (a), (b), and (c) is taken to maintain the copper concentration in the chlorine leaching solution in the range of 10 g / L to 60 g / L.
(Record)
(A) Copper supplementation means for increasing the copper concentration in the chlorine leachate by bringing the copper leachate having a redox potential of 400 mV (Ag / AgCl electrode standard) or more into contact with metallic copper.
(B) Decoppering means for reducing the copper concentration in the chlorine leaching solution by reducing the chlorine leaching solution to reduce the copper ion concentration having a valence of 2 and then collecting the leached chlorine leaching solution by copper electrolysis. .
(C) Neutral means that does not implement (i) or (b) above.

本発明のニッケル硫化物原料の処理方法によれば、ニッケルを含む複数種の金属硫化物の原料処理比率の調整を容易にかつ安定的に行うことができる。
そして、ニッケルを含む複数種の金属硫化物の原料処理比率の調整を容易にかつ安定的に行うことによって、混合硫化物の処理量減少による電気ニッケルの減産回避、混合硫化物の増処理による電気ニッケルの増産が達成できる。
また、不純物負荷調整のための原料の処理比率調整を容易に実施することが可能となり、塩素浸出プロセス操業の安定化を達成することができる。
According to the nickel sulfide raw material treatment method of the present invention, the raw material treatment ratio of a plurality of types of metal sulfides containing nickel can be adjusted easily and stably.
And by adjusting the raw material treatment ratio of multiple types of metal sulfides containing nickel easily and stably, avoiding reduction in production of electric nickel by reducing the amount of mixed sulfide treated, and electricity by increasing the treatment of mixed sulfide Increase in nickel production can be achieved.
Further, it is possible to easily adjust the raw material processing ratio for adjusting the impurity load, and it is possible to achieve stabilization of the chlorine leaching process operation.

電気ニッケルの生産量を100としたときの塩素ガス量、原料中のニッケル量の当量比のイメージを表した、特許文献1に係る塩素浸出プロセスの工程図である。It is a flowchart of the chlorine leaching process concerning patent documents 1 showing the image of the equivalent ratio of the amount of chlorine gas when the amount of production of electric nickel is 100, and the amount of nickel in a raw material. 電気ニッケルの生産量を100としたときの塩素ガス量、原料中のニッケル量の当量比のイメージを表した、特許文献2に係る塩素浸出プロセスの工程図である。It is a flowchart of the chlorine leaching process concerning patent documents 2 showing the image of the equivalent ratio of the amount of chlorine gas when the amount of production of electric nickel is 100, and the amount of nickel in a raw material. 塩素浸出液中の銅濃度を高く維持したときの、電気ニッケルの生産量を100としたときの塩素ガス量、原料中のニッケル量の当量比のイメージを表した、特許文献2に係る塩素浸出プロセスの工程図である。A chlorine leaching process according to Patent Document 2 showing an image of an equivalent ratio of the chlorine gas amount and the nickel amount in the raw material when the production amount of electric nickel is 100 when the copper concentration in the chlorine leaching solution is kept high FIG. 電気ニッケルの生産量を100としたときの塩素ガス量、原料中のニッケル量の当量比のイメージを表した、本発明に係る塩素浸出プロセスの工程図である。It is process drawing of the chlorine leaching process concerning the present invention showing the image of the equivalent ratio of the amount of chlorine gas when the amount of production of electric nickel is 100, and the amount of nickel in a raw material. 塩素浸出液中の銅濃度と混合硫化物処理比率の関係を示した図である。It is the figure which showed the relationship between the copper concentration in a chlorine leaching solution, and a mixed sulfide process ratio. 本発明に係る銅濃度調整工程の概略フローシートである。(a)は塩素浸出液の銅濃度を低下させる場合、(b)は塩素浸出液の銅濃度を上昇させる場合のフローシートである。It is a general | schematic flow sheet of the copper concentration adjustment process which concerns on this invention. (A) is a flow sheet when lowering the copper concentration of the chlorine leachate, and (b) is a flow sheet when increasing the copper concentration of the chlorine leachate. 本発明によって操業を行った時の、塩素浸出液の銅濃度と混合硫化物の処理比率の推移を示した図である。It is the figure which showed transition of the copper concentration of a chlorine leaching solution, and the processing rate of a mixed sulfide when it operates by this invention.

以下に、本発明に係る塩素浸出液の銅濃度の管理基準値の設定方法、設定された管理基準値の銅濃度調整方法を含む塩素浸出法によるニッケルの湿式精錬プロセスを踏まえてニッケル硫化物原料の処理方法に関し、詳細に説明する。   In the following, based on a nickel sulfide raw material refining process based on a nickel refining process by a chlorine leaching method including a method for setting a copper concentration control method for a chlorine leachate according to the present invention, and a copper concentration adjusting method for a set control reference value. The processing method will be described in detail.

本発明は、ニッケルを製造する湿式製錬プロセスにおけるニッケル硫化物原料の処理方法で、ニッケルを含む金属硫化物、又はその硫化物と下記セメンテーション残渣を塩素浸出用ニッケル原料として用い、前記塩素浸出用ニッケル原料に含まれるニッケル及び不純物を、塩化物水溶液中に塩素浸出して塩素浸出液を得る塩素浸出工程、ニッケルを含む金属硫化物に塩素浸出液を接触させることで塩素浸出液中の2価銅イオンによりニッケルを含む金属硫化物中のニッケルを置換浸出すると共に硫化銅等を生成させて銅が除去された置換浸出終液と硫化銅等を含むセメンテーション残渣を得る置換浸出工程、置換浸出終液中の不純物を除去して塩化ニッケル溶液を得る浄液工程、塩化ニッケル溶液から電解採取法によって金属ニッケルと塩素ガスを回収する電解工程を含むニッケル硫化物原料の処理方法において、下記(1)から(3)に示す手順に従って、前記塩素浸出液中の銅濃度の管理基準値(A)を低下させることによって、亜硫化ニッケルと金属ニッケルを含むニッケルマットの処理量(B)と、硫化ニッケルと硫化コバルトを含む混合硫化物の処理量(C)との合計原料処理量(B+C)に対する、硫化ニッケルと硫化コバルトを含む混合硫化物処理量(C)の処理比率(D=C÷(B+C)×100%)を上昇させることを特徴とする。   The present invention relates to a method for treating nickel sulfide raw material in a hydrometallurgical process for producing nickel, using a metal sulfide containing nickel, or a sulfide thereof and the following cementation residue as a nickel raw material for chlorine leaching, Chlorine leaching process in which nickel and impurities contained in nickel raw material are leached into chloride aqueous solution to obtain chlorine leaching solution, and divalent copper ions in chlorine leaching solution are brought into contact with metal sulfide containing nickel The substitution leaching process, in which nickel in metal sulfides containing nickel is replaced and leached and copper sulfide is generated to obtain a cementation residue containing copper sulfide and the like. Process of removing nickel impurities and obtaining nickel chloride solution, nickel nickel and chlorine by electrowinning from nickel chloride solution In the nickel sulfide raw material processing method including the electrolytic step of recovering the catalyst, by reducing the control standard value (A) of the copper concentration in the chlorine leachate according to the procedure shown in (1) to (3) below, Nickel sulfide and cobalt sulfide relative to the total raw material throughput (B + C) of nickel matte containing nickel sulfide and nickel (B) and mixed sulfide containing nickel sulfide and cobalt sulfide treated (C) The processing ratio (D = C ÷ (B + C) × 100%) of the mixed sulfide processing amount (C) containing is increased.

(1)ニッケルマットの処理量(B)から許容可能な塩素浸出液中の銅負荷(A1)および塩素浸出液中の銅濃度の上限値(A2)(単位は[g/L])を決定する。
(2)塩素浸出液中の銅濃度の上限値(A2)に対する混合硫化物処理量の処理比率(D)(単位は[%])との関係式(D=f(A2))を導き出す。
(3)関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))と、前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))をD軸に沿って−10移動した式(D+10=f(A2+5))と、式A2=15と、式A2=55に囲まれた範囲にある混合硫化物処理量の処理比率(D)に対応した塩素浸出液中の銅濃度の管理基準値(A)を設定する。
(1) The allowable copper load (A1) in the chlorine leachate and the upper limit (A2) of the copper concentration in the chlorine leachate (unit: [g / L]) are determined from the nickel mat throughput (B).
(2) A relational expression (D = f (A2)) with the treatment ratio (D) (unit: [%]) of the mixed sulfide treatment amount with respect to the upper limit (A2) of the copper concentration in the chlorine leachate is derived.
(3) The relational expression (D = f (A2)) is moved by -5 along the A2 axis (D = f (A2 + 5)) and the relational expression (D = f (A2)) along the A2 axis. The range surrounded by the equation (D + 10 = f (A2 + 5)), the equation (D + 10 = f (A2 + 5)) moved by −10 along the D axis, the equation A2 = 15, and the equation A2 = 55. The control standard value (A) of the copper concentration in the chlorine leaching solution corresponding to the processing ratio (D) of the mixed sulfide processing amount in (1) is set.

また、本発明のニッケル硫化物原料の処理方法は、ニッケルを含む金属硫化物からニッケルを塩化物水溶液中に塩素浸出して塩素浸出液を得る塩素浸出工程により得られた塩素浸出液に含まれる銅の濃度を、銅濃度調整工程において前記管理基準値(A)に基づいて調節した塩素浸出液を得ることを特徴とするニッケル硫化物原料の処理方法であって、その銅濃度調製工程は、塩素浸出液の銅濃度の管理基準値に対する銅濃度挙動によって以降の採りうる手段を予め定め、その定められた手段に沿って実施することにより塩素浸出液中の銅濃度を10g/L以上60g/L以下の範囲に維持することを特徴とするものである。   The nickel sulfide raw material treatment method of the present invention also includes a copper leaching solution obtained by a chlorine leaching step obtained by leaching nickel from a metal sulfide containing nickel into a chloride aqueous solution to obtain a chlorine leaching solution. A method for treating a nickel sulfide raw material characterized in that a chlorine leachate whose concentration is adjusted based on the control reference value (A) in a copper concentration adjustment step is obtained, wherein the copper concentration preparation step Based on the copper concentration behavior with respect to the control value of copper concentration, the means that can be taken thereafter are determined in advance, and the copper concentration in the chlorine leachate is set in the range of 10 g / L or more and 60 g / L or less by carrying out along the determined means. It is characterized by maintaining.

下記に、管理基準値に対する銅濃度挙動[a]から[d]を表1に、それぞれの銅挙動に対応して予め定められた採りうる手段を表2に示す。   The copper concentration behaviors [a] to [d] with respect to the management reference value are shown in Table 1 below, and the means that can be taken in advance corresponding to each copper behavior are shown in Table 2.

1.ニッケルおよびコバルト製錬プロセス
本発明を含むニッケルおよびコバルト製錬プロセスの概略工程図を図4に示す。
本発明は、塩素浸出工程を含むニッケルの湿式製錬プロセスの全体工程の中の、ニッケルを含む金属硫化物からニッケルを水溶液中に塩素浸出して塩素浸出液を得る方法にあって、塩素浸出液中の銅濃度の設定方法と銅濃度の調整方法に関する技術ではあるが、ニッケル製錬プロセスにおける原料処理の全体最適化を達成するための技術であるため、本発明に特に関係する、原料、塩素浸出、置換浸出(セメンテーション)について詳細に説明する。
1. Nickel and Cobalt Smelting Process A schematic process diagram of the nickel and cobalt smelting process including the present invention is shown in FIG.
The present invention relates to a method for obtaining a chlorine leachate by leaching nickel into an aqueous solution from a metal sulfide containing nickel in the entire process of a nickel hydrometallurgical process including a chlorine leaching process, Although it is a technology related to the copper concentration setting method and the copper concentration adjustment method, it is a technology for achieving the overall optimization of the raw material treatment in the nickel smelting process, and is therefore particularly relevant to the present invention. The replacement leaching (cementation) will be described in detail.

(1)原料
主要な原料は、ニッケルマットと混合硫化物の2種類となる。
ニッケルマットとは、ニッケル硫化鉱石を溶鉱炉で溶解して得られるニッケル硫化物や、ニッケル酸化鉱石に硫黄を添加して電気炉で溶解して得られるニッケル硫化物等、いわゆる乾式製錬法で得られたニッケル硫化物を指している。
このニッケルマットの主成分は、NiとNi(金属ニッケル)であり、そのおおよその化学組成は、Niが65〜80重量%、Coが約1重量%、Cuが0.1〜4重量%、Feが0.1〜5重量%、Sが18〜25重量%である。
(1) Raw materials There are two main raw materials: nickel matte and mixed sulfide.
Nickel matte is obtained by so-called dry smelting methods such as nickel sulfide obtained by melting nickel sulfide ore in a smelting furnace, nickel sulfide obtained by adding sulfur to nickel oxide ore and melting in an electric furnace. Refers to nickel sulfide.
The main components of this nickel mat are Ni 3 S 2 and Ni 0 (metallic nickel). The approximate chemical composition is 65 to 80% by weight of Ni, about 1% by weight of Co, and 0.1 to 9% of Cu. 4 wt%, Fe is 0.1 to 5 wt%, and S is 18 to 25 wt%.

ニッケル酸化鉱石を原料としたニッケルマットと比較して、ニッケル硫化鉱石を原料としたニッケルマットは銅をはじめとする不純物の含有量が高いという特徴があり、ニッケル製錬プロセスへの主な不純物のインプット源は、ニッケル硫化鉱石を原料としたニッケルマットである。   Compared to nickel matte made from nickel oxide ore, nickel matte made from nickel sulfide ore is characterized by a high content of impurities, including copper, and is a major impurity in the nickel smelting process. The input source is nickel mat made from nickel sulfide ore.

したがって、このニッケル硫化鉱石を原料としたニッケルマットの処理量によって、銅をはじめとする不純物のインプット量が大きく変動することになるため、塩素浸出工程を含むニッケルの湿式製錬プロセスへの不純物負荷を制限するためには、ニッケル硫化鉱石を原料としたニッケルマットの処理比率を下げて混合硫化物やニッケル酸化鉱石を原料としたニッケルマットの処理比率を上げる必要がある。   Therefore, the amount of impurities input, including copper, varies greatly depending on the amount of nickel matte processed from this nickel sulfide ore, so the impurity load on the nickel hydrometallurgical process including the chlorine leaching process In order to limit this, it is necessary to lower the treatment ratio of nickel matte made from nickel sulfide ore and increase the treatment ratio of nickel mat made from mixed sulfide or nickel oxide ore.

一方で、混合硫化物とは、低ニッケル品位のニッケル酸化鉱石を加圧酸浸出し、その加圧酸浸出液から鉄をはじめとする不純物を除去した後、湿式硫化反応によって、例えば硫化水素ガスをニッケルイオン及びコバルトイオンを含んだ浸出液中に吹込むことによって、得られたニッケルおよびコバルトを含む混合硫化物を指している。   On the other hand, mixed sulfide means low-nickel grade nickel oxide ore under pressure acid leaching, impurities such as iron are removed from the pressure acid leaching solution, and then hydrogen sulfide gas, for example, is obtained by wet sulfidation reaction. It refers to a mixed sulfide containing nickel and cobalt obtained by blowing into a leachate containing nickel ions and cobalt ions.

混合硫化物の主成分はNiSとCoSであり、そのおおよその化学組成は、Niが55〜60重量%、Coが3〜6重量%、Cuが0.1重量%未満、Feが0.1〜1重量%、Sが30〜35重量%である。
近年、コスト的に有利な原料として前記混合硫化物の増産が図られており、混合硫化物の増処理、すなわち混合硫化物の処理比率の増加が求められている。
The main components of the mixed sulfide are NiS and CoS, and their approximate chemical compositions are 55-60% by weight of Ni, 3-6% by weight of Co, less than 0.1% by weight of Cu, and 0.1% of Fe. -1% by weight, S 30-35% by weight.
In recent years, production of the mixed sulfide has been increased as a cost-effective raw material, and increased treatment of the mixed sulfide, that is, increased treatment ratio of the mixed sulfide is required.

(2)塩素浸出
混合硫化物および後述するセメンテーション残渣を、塩化物水溶液にレパルプした後、そのスラリーに塩素ガスを吹込むことによって混合硫化物中のニッケルおよびコバルトと、セメンテーション残渣中のニッケルおよび銅を、塩化物水溶液中に塩素浸出して塩素浸出液を得る。
(2) Chlorine leaching The mixed sulfide and cementation residue described later are repulped into an aqueous chloride solution, and then the nickel and cobalt in the mixed sulfide and nickel in the cementation residue are blown into the slurry by injecting chlorine gas. And copper is leached into an aqueous chloride solution to obtain a chlorine leaching solution.

この工程では、2価の銅のクロロ錯イオンが混合硫化物やセメンテーション残渣中の金属を溶解するための直接的な浸出剤として作用し、塩素ガスは銅の1価イオンを2価イオンに酸化することにより間接的に浸出反応に関与する。
その主要な塩素浸出反応式を下記式(1)〜式(4)に示す。
In this process, divalent copper chloro complex ions act as a direct leaching agent to dissolve mixed sulfides and metals in cementation residues, and chlorine gas turns copper monovalent ions into divalent ions. It is indirectly involved in the leaching reaction by oxidation.
The main chlorine leaching reaction formulas are shown in the following formulas (1) to (4).

塩素浸出反応条件は、反応時の塩化ニッケル水溶液の酸化還元電位が480〜560mV、温度が105〜115℃である。
この浸出反応が効率的に進行するためには、塩素浸出液中の銅濃度が10g/L以上であることが条件であり、その銅濃度が高いほど塩素吸収効率が高くなるため、金属成分の浸出率が向上する。
As for the chlorine leaching reaction conditions, the oxidation-reduction potential of the nickel chloride aqueous solution during the reaction is 480 to 560 mV, and the temperature is 105 to 115 ° C.
In order for this leaching reaction to proceed efficiently, the copper concentration in the chlorine leaching solution is 10 g / L or more, and the higher the copper concentration, the higher the chlorine absorption efficiency. The rate is improved.

塩素浸出液中の銅濃度が10g/L未満に低下した場合、1価の銅クロロ錯イオンによる塩素ガスの気液吸収能力が低下するため、未反応の塩素ガスが大量に塩素浸出反応槽の気相部に放出されることになる。   When the copper concentration in the chlorine leachate is reduced to less than 10 g / L, the gas-liquid absorption capacity of the monovalent copper chloro complex ion is reduced, so a large amount of unreacted chlorine gas is generated in the chlorine leach reaction tank. It will be released to the phase.

このことは、塩素ガスのロスが増加してコストが増加するだけに止まらず、浸出残渣に残留するニッケルおよびコバルトが増加し、ニッケルおよびコバルトの浸出率が低下して、ニッケルおよびコバルトの実収率が低下することに繋がる。加えて、上記の問題により、塩素ガスの吹込み量を減らして原料処理量を減らす操作を行わざるを得ないため、ニッケルの生産量が減少する。
また、環境問題にもつながる可能性もある。さらに、巨大な塩素ガス吸収装置と多量の吸収液を必要とするため、現実的には工業的な操業が不可能となる。
This is not only an increase in cost due to an increase in chlorine gas loss, but also an increase in nickel and cobalt remaining in the leaching residue, a decrease in the leaching rate of nickel and cobalt, and an actual yield of nickel and cobalt. Leads to a decline. In addition, due to the above problem, the operation of reducing the amount of raw material processing by reducing the amount of chlorine gas blown must be performed, so that the amount of nickel produced decreases.
It may also lead to environmental problems. Furthermore, since a huge chlorine gas absorption device and a large amount of absorption liquid are required, it is practically impossible to perform an industrial operation.

一方、塩素浸出液中の銅濃度が60g/Lを超えると、浸出反応自体には有利に働くが、その反面で過剰に反応が促進されて析出する硫黄の酸化や反応界面への融着を進め、逆に浸出率を低下させる。また、置換浸出工程では塩素浸出液中の銅イオンの除去も同時に行われているため、必要なニッケルマット量が増加すると共にセメンテーション残渣量が増加する。
この置換浸出工程でのセメンテーション残渣量の増加は、固液分離等、そのハンドリングに手間を要すことになり、効率的では無い。
On the other hand, if the copper concentration in the chlorine leaching solution exceeds 60 g / L, the leaching reaction itself works favorably, but on the other hand, the reaction is promoted excessively and oxidation of the precipitated sulfur and fusion to the reaction interface are promoted. Conversely, the leaching rate is reduced. In addition, since the copper ions in the chlorine leaching solution are simultaneously removed in the substitution leaching step, the necessary nickel mat amount increases and the cementation residue amount increases.
Increasing the amount of cementation residue in this substitution leaching process is not efficient because it requires troublesome handling such as solid-liquid separation.

以上は、必要なニッケルマット量が確保できた場合の問題点であるが、必要なニッケルマット量が確保できない場合には、置換浸出工程での脱銅が十分に行われず、置換浸出終液の銅濃度が上昇して、次の浄液工程への脱銅負荷の上昇、さらには電気ニッケルへの銅の混入を引き起こし、電気ニッケルの製造そのものが成り立たなくなる。   The above is a problem when the necessary amount of nickel mat can be ensured. However, when the necessary amount of nickel mat cannot be ensured, copper removal is not sufficiently performed in the replacement leaching process, and the replacement leaching final solution is not enough. The copper concentration increases, causing an increase in the decoppering load to the next liquid purification process, and further causing the copper to be mixed into the electric nickel, so that the production of the electric nickel itself cannot be realized.

そこで、塩素浸出液中の銅濃度は60g/L以下に維持する必要がある。
そのため、原料処理比率に応じて、塩素浸出液の銅濃度が10〜60g/Lの範囲内になるように塩素浸出液の銅濃度の管理基準値を変化させることが本発明の主旨であり、この塩素浸出液中の銅濃度の調整が、本発明の銅濃度調整工程において行われる。
Therefore, it is necessary to maintain the copper concentration in the chlorine leaching solution at 60 g / L or less.
Therefore, the main point of the present invention is to change the control reference value of the copper concentration of the chlorine leachate so that the copper concentration of the chlorine leachate falls within the range of 10 to 60 g / L according to the raw material treatment ratio. Adjustment of the copper concentration in the leachate is performed in the copper concentration adjusting step of the present invention.

塩素浸出液中の銅濃度の増減は、銅濃度を増加させる場合は、塩素浸出液と金属銅を接触させる方法または銅電解採取の停止によって行い、一方で銅濃度を低下させる場合には、銅電解採取によって銅粉を抜出す方法によって実施される。   When increasing the copper concentration, increase or decrease the copper concentration in the chlorine leaching solution by contacting the chlorine leaching solution with metallic copper or by stopping the copper electrowinning, while reducing the copper concentration, Is carried out by a method of extracting copper powder.

(3)置換浸出(セメンテーション)
置換浸出工程は、第1の置換浸出工程と第2の置換浸出工程(図2、図3、図4では図示せず)の、2つのステージで構成される。
(3) Replacement leaching (cementation)
The replacement leaching process includes two stages, a first replacement leaching process and a second replacement leaching process (not shown in FIGS. 2, 3, and 4).

先ず、塩素浸出液に含まれる2価の銅のクロロ錯イオンの酸化力を使って、第1の置換浸出工程を実施して混合硫化物中のニッケルおよびコバルトを浸出する。
この第1の置換浸出工程で得られた置換浸出液は2価の銅クロロ錯イオンの一部が1価の銅のクロロ錯イオンに還元されている。
First, using the oxidizing power of divalent copper chloro complex ions contained in the chlorine leaching solution, the first substitution leaching step is performed to leach nickel and cobalt in the mixed sulfide.
In the substitution leachate obtained in the first substitution leaching step, a part of the divalent copper chloro complex ion is reduced to a monovalent copper chloro complex ion.

次に、第2の置換浸出工程の実施により当該置換浸出液とニッケルマットを接触させることにより、置換浸出液中の銅イオンとニッケルマット中のニッケルのセメンテーション反応が行われる。
主要な置換浸出反応式を下記式(5)〜式(7)に示す。
Next, by carrying out the second substitution leaching step, the substitution leaching solution and the nickel mat are brought into contact with each other, whereby a cementation reaction between the copper ions in the substitution leaching solution and the nickel in the nickel mat is performed.
The main substitution leaching reaction formulas are shown in the following formulas (5) to (7).

置換浸出反応条件は、反応時の塩化ニッケル水溶液の酸化還元電位が50〜300mV、温度が70〜100℃である。
この置換浸出終液の銅濃度を低下させるためには、混合硫化物中に含まれるNiSよりも還元力の強いNi(金属ニッケル)やNiを含有したニッケルマットが必要となる。
As for the substitution leaching reaction conditions, the oxidation-reduction potential of the nickel chloride aqueous solution during the reaction is 50 to 300 mV, and the temperature is 70 to 100 ° C.
In order to reduce the copper concentration of the substitution leaching final solution, a nickel mat containing Ni 0 (metallic nickel) or Ni 3 S 2 having a reducing power stronger than NiS contained in the mixed sulfide is required.

混合硫化物とニッケルマットの不溶解残渣とセメンテーション反応によって得られた銅を含んだ固体を含む、セメンテーション残渣は、第2の置換浸出工程で得られた置換浸出終液と固液分離された後、塩素浸出工程に送られる。
このセメンテーション反応は、固体のニッケルが溶出してニッケルイオンとなり、その溶出したニッケルと電気化学的に当量の液中の銅イオンが固体となるため、置換浸出工程は塩素浸出液中に含まれる銅を固体として除去する脱銅工程であるとも言える。
The cementation residue containing the insoluble residue of mixed sulfide and nickel matte and the solid containing copper obtained by the cementation reaction is solid-liquid separated from the substitution leaching final solution obtained in the second substitution leaching step. And then sent to the chlorine leaching process.
In this cementation reaction, solid nickel elutes into nickel ions, and copper ions in the liquid that is electrochemically equivalent to the eluted nickel become solids, so the substitution leaching step is the copper contained in the chlorine leachate. It can also be said that this is a copper removal step of removing as solid.

置換浸出液中の銅イオンはCuSまたはCuメタルの形態となって固体となるため、第2の置換浸出工程で得られる置換浸出終液中の銅濃度は0.02g/L以下となる。 Since the copper ions in the substitution leaching solution are in the form of Cu 2 S or Cu metal and become a solid, the copper concentration in the substitution leaching final solution obtained in the second substitution leaching step is 0.02 g / L or less.

2.塩素浸出液の銅濃度の設定方法
前述のように、塩素浸出液中の銅濃度が増加すると置換浸出工程での必要なニッケルマットの処理量が増加するため、相対的に混合硫化物処理量が減少し、混合硫化物処理比率が低下する。
2. Setting method of copper concentration in chlorine leachate As mentioned above, the amount of nickel matte required in the substitution leach process increases as the copper concentration in the chlorine leachate increases, so the mixed sulfide treatment amount decreases relatively. , Mixed sulfide treatment ratio decreases.

逆に、塩素浸出液中の銅濃度が減少すると置換浸出工程での必要なニッケルマットの処理量が減少するため、相対的に混合硫化物処理量が増加し、混合硫化物処理比率が上昇する。
言い換えれば、塩素浸出液中の銅濃度によって、同じニッケルを含む硫化物原料であるが含まれる化合物種の異なる、ニッケルマットと混合硫化物の処理比率の変更可能な範囲が決まってくる。
Conversely, if the copper concentration in the chlorine leaching solution decreases, the amount of nickel matte required in the substitution leaching step decreases, so the mixed sulfide treatment amount increases relatively and the mixed sulfide treatment ratio increases.
In other words, depending on the copper concentration in the chlorine leaching solution, the range in which the treatment ratio of the nickel mat and the mixed sulfide, which are sulfide raw materials containing the same nickel, but containing different compound types, is determined.

本発明は、このニッケルマットの処理量(B)と混合硫化物の処理量(C)との合計原料処理量に対する、混合硫化物処理量の処理比率(D)に応じて、塩素浸出液の銅濃度の管理基準値(A)を調整する手順を定めたものである。
その手順を、以下(1)〜(2)に説明する。
The present invention provides a copper leaching solution according to the treatment ratio (D) of the mixed sulfide treatment amount to the total raw material treatment amount of the nickel matte treatment amount (B) and the mixed sulfide treatment amount (C). The procedure for adjusting the density management reference value (A) is defined.
The procedure will be described below in (1) to (2).

(1)まず、図1〜4に示した通り、電気ニッケルの生産量から必要な合計原料処理量が決まる。ここで、合計原料処理量に対する混合硫化物処理量の処理比率(D)によって、ニッケルマットの処理量(B)が決まる。 (1) First, as shown in FIGS. 1 to 4, the required total raw material processing amount is determined from the production amount of electro nickel. Here, the processing amount (B) of the nickel mat is determined by the processing ratio (D) of the mixed sulfide processing amount with respect to the total raw material processing amount.

次に、ニッケルマットの処理量(B)から許容可能な塩素浸出液中の銅負荷(A1)を決定する。
ここで、例えば、置換浸出工程にて最低限必要となるニッケルマット量は、塩素浸出液中の銅イオンに対する重量比率で1.2(ニッケルマット中の金属ニッケル量/塩素浸出液中の銅イオン量)の金属ニッケルが含まれるニッケルマット量であることが実験的に確認されており、そのようにして求めたパラメーターを使用することが好ましい。
Next, the allowable copper load (A1) in the chlorine leachate is determined from the nickel mat throughput (B).
Here, for example, the minimum amount of nickel mat required in the substitution leaching step is 1.2 (the amount of nickel metal in the nickel mat / the amount of copper ions in the chlorine leaching solution) by weight ratio to the copper ions in the chlorine leaching solution. It has been experimentally confirmed that the amount of the nickel matte containing the metallic nickel is preferable, and it is preferable to use the parameters thus determined.

許容可能な塩素浸出液中の銅負荷(A1)から塩素浸出液の銅濃度の上限値(A2)を決定する。
塩素浸出液の銅濃度の上限値(A2)は、許容可能な塩素浸出液中の銅負荷(A1)を塩素浸出液の流量で除することによって求めることができる。
なお、塩素浸出液の流量は、例えば、必要な合計原料処理量を、塩素浸出と置換浸出工程における浸出前後のニッケル濃度の上昇値で除することによって求めることができる。この塩素浸出液の流量は、基本的にはニッケル生産量に比例するので、適当なパラメーターを設定しても良い。
The upper limit (A2) of the copper concentration of the chlorine leachate is determined from the allowable copper load (A1) in the chlorine leachate.
The upper limit (A2) of the copper concentration of the chlorine leachate can be determined by dividing the allowable copper load (A1) in the chlorine leachate by the flow rate of the chlorine leachate.
The flow rate of the chlorine leaching solution can be obtained, for example, by dividing the required total raw material throughput by the increase value of the nickel concentration before and after leaching in the chlorine leaching and substitution leaching steps. Since the flow rate of the chlorine leaching solution is basically proportional to the nickel production amount, an appropriate parameter may be set.

前述のようにして決定した塩素浸出液の銅濃度の上限値(A2)と混合硫化物処理量の処理比率(D)の関係式(D=f(A2))を導き出す。
関係式(D=f(A2))は、計算により求めても良いし、A2とDを何点か求めた後、そのデータを統計解析することにより求めても良い。
A relational expression (D = f (A2)) between the upper limit (A2) of the copper concentration of the chlorine leaching solution determined as described above and the treatment ratio (D) of the mixed sulfide treatment amount is derived.
The relational expression (D = f (A2)) may be obtained by calculation, or after obtaining several points of A2 and D, the data may be obtained by statistical analysis.

(2)塩素浸出液の銅濃度の上限値(A2)と混合硫化物処理量の処理比率(D)で形成するA2−D直交座標上で、関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))と、前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))をD軸に沿って−10移動した式(D+10=f(A2+5))と、式A2=15と、式A2=55に囲まれた範囲にある混合硫化物処理量の処理比率(D)に対応した塩素浸出液中の銅濃度の管理基準値(A)を設定する。 (2) The relational expression (D = f (A2)) is represented by the A2 axis on the A2-D orthogonal coordinate formed by the upper limit (A2) of the copper concentration of the chlorine leachate and the treatment ratio (D) of the mixed sulfide treatment amount. The equation (D = f (A2 + 5)) moved by -5 along the line A and the equation (D = f (A2 + 5)) moved -5 along the axis A2 by the relational expression (D = f (A2 + 5)) and D Corresponding to the treatment ratio (D) of the mixed sulfide treatment amount in the range surrounded by the equation (D + 10 = f (A2 + 5)) moved by −10 along the axis, the equation A2 = 15, and the equation A2 = 55 Set the control standard value (A) for the copper concentration in the chlorine leachate.

本発明の手順に基づいた一実施例としての、塩素浸出液中の銅濃度の管理基準値(A)の設定領域を図5に示した。   FIG. 5 shows a setting region of the control reference value (A) of the copper concentration in the chlorine leaching solution as an example based on the procedure of the present invention.

塩素浸出液中の銅イオンに対する重量比率で1.2に相当するニッケルマット量より少ないニッケルマット量を置換浸出工程で処理する場合、置換浸出工程での脱銅が十分に行われず、置換浸出終液の銅濃度が上昇して、次の浄液工程への脱銅負荷の上昇、さらには電気ニッケルへの銅の混入を引き起こし、電気ニッケルの製造そのものが成り立たなくなる。
そこで、塩素浸出液の銅濃度の管理基準値の上限値(A)は塩素浸出液の銅濃度の上限値(A2)−5g/Lとした。
When a nickel mat amount less than the nickel mat amount corresponding to 1.2 in terms of weight ratio to the copper ions in the chlorine leachate is treated in the substitution leaching step, the copper leaching in the substitution leaching step is not sufficiently performed, and the substitution leaching final solution As a result, the copper concentration of the copper increases, the copper removal load increases in the next liquid purification process, and the copper is mixed into the electric nickel.
Therefore, the upper limit value (A) of the control standard value of the copper concentration of the chlorine leachate was set to the upper limit value (A2) −5 g / L of the copper concentration of the chlorine leach solution.

また、前述のように、混合硫化物処理量の処理比率(D)は高い方が望ましく、混合硫化物処理量の処理比率(D)の下限値は、混合硫化物処理量の処理比率(D)の上限値−10%とした。   Further, as described above, it is desirable that the treatment ratio (D) of the mixed sulfide treatment amount is high, and the lower limit value of the treatment ratio (D) of the mixed sulfide treatment amount is the treatment ratio (D) of the mixed sulfide treatment amount. ) Was set to 10%.

図5によれば、塩素浸出液中の銅濃度が約80g/Lの場合、混合硫化物処理比率の上限は約25%に止まり、それ以上混合硫化物処理比率を増加させることはできない。しかしながら、銅濃度を約35g/Lまで低下させると、混合硫化物処理比率を約60%程度まで増加させることが可能となり、混合硫化物の増処理を図ることができる。
なお、本発明によれば、混合硫化物処理量の処理比率(D)の調整を容易にかつ安定的に行うことができる。
According to FIG. 5, when the copper concentration in the chlorine leachate is about 80 g / L, the upper limit of the mixed sulfide treatment ratio is only about 25%, and the mixed sulfide treatment ratio cannot be further increased. However, when the copper concentration is reduced to about 35 g / L, the mixed sulfide treatment ratio can be increased to about 60%, and the mixed sulfide can be increased.
According to the present invention, the treatment ratio (D) of the mixed sulfide treatment amount can be adjusted easily and stably.

そして、混合硫化物処理量の処理比率(D)の調整を容易にかつ安定的に行うことによって、例えば、置換浸出終液の銅濃度上昇による操業停止や塩素浸出工程におけるニッケル浸出率の低下等の重大トラブルや、混合硫化物の処理量減少による電気ニッケルの減産を回避することができ、混合硫化物の増処理による電気ニッケルの増産も達成できる。   And by adjusting the treatment ratio (D) of the mixed sulfide treatment amount easily and stably, for example, the operation is stopped due to an increase in the copper concentration of the substitution leaching final solution, the nickel leaching rate is lowered in the chlorine leaching process, etc. Therefore, it is possible to avoid the production of nickel and the production of mixed sulfide.

3.塩素浸出液の銅濃度の調整方法
図6に本発明に係る銅濃度調整工程の概略フローシートを示す。
図6に示した概略フローシートのうち、(a)は塩素浸出液の銅濃度を低下させる場合のフローシートである。(b)は塩素浸出液の銅濃度を上昇させる場合のフローシートである。
3. Method for Adjusting Copper Concentration of Chlorine Leaching Solution FIG. 6 shows a schematic flow sheet of the copper concentration adjusting step according to the present invention.
Among the schematic flow sheets shown in FIG. 6, (a) is a flow sheet in the case of reducing the copper concentration of the chlorine leaching solution. (B) is a flow sheet for increasing the copper concentration of the chlorine leaching solution.

まず図6(a)の工程について説明する。
塩素浸出工程で発生した塩素浸出液の一部を、金属ニッケルが充填されたカラム槽に通液して、塩素浸出液中の2価の銅クロロ錯イオンの一部を1価の銅クロロ錯イオンに還元する。
塩素浸出液の組成は、Ni濃度が200〜250g/L、Cu濃度が10〜60g/Lである。
この還元工程で、酸化還元電位400〜500mV、2価銅比((Cu2+濃度/全Cu濃度)×100%)60〜80%の塩素浸出液が、酸化還元電位380〜480mV、2価銅比10〜30%に還元される。
First, the process of FIG. 6A will be described.
Part of the chlorine leaching solution generated in the chlorine leaching process is passed through a column tank filled with metallic nickel, and part of the divalent copper chloro complex ions in the chlorine leaching solution is converted to monovalent copper chloro complex ions. Reduce.
The composition of the chlorine leaching solution has a Ni concentration of 200 to 250 g / L and a Cu concentration of 10 to 60 g / L.
In this reduction step, a chlorine leaching solution having a redox potential of 400 to 500 mV and a divalent copper ratio ((Cu 2+ concentration / total Cu concentration) × 100%) of 60 to 80% becomes a redox potential of 380 to 480 mV and a divalent copper ratio. Reduced to 10-30%.

次に、前記還元処理後の塩素浸出液にニッケル電解廃液を混合し、脱銅電解給液の銅濃度調整を行う。
脱銅電解給液の銅濃度は、15〜25g/Lに調整する。
その後、脱銅電解給液を電解槽に供給し、不溶性アノードを用いた電解採取法によって、銅粉として銅を電解採取する。
Next, a nickel electrolytic waste solution is mixed with the chlorine leaching solution after the reduction treatment, and the copper concentration of the copper removal electrolytic feed solution is adjusted.
The copper concentration of the copper removal electrolytic feed solution is adjusted to 15 to 25 g / L.
Thereafter, a copper removal electrolytic feed solution is supplied to the electrolytic cell, and copper is electrolytically collected as a copper powder by an electrolytic collection method using an insoluble anode.

電解条件は、通電電流が11000〜14000A/槽、電流密度が280〜360A/m、脱銅電解給液量が20L/分・槽、脱銅電解廃液のCu濃度が10〜15g/Lである。 The electrolysis conditions are as follows: the energization current is 11000-14000 A / tank, the current density is 280-360 A / m 2 , the copper removal electrolysis supply amount is 20 L / min / tank, and the Cu concentration of the copper removal electrolysis waste liquid is 10-15 g / L. is there.

脱銅電解槽底から抜き取った銅粉スラリーは、遠心分離機で脱水され、銅粉は銅製錬系に払出される。
脱銅電解廃液および銅粉スラリーの脱水ろ液は、置換浸出工程に供給される。
The copper powder slurry extracted from the bottom of the copper removal electrolysis tank is dehydrated by a centrifugal separator, and the copper powder is discharged to a copper smelting system.
The copper removal electrolysis waste liquid and the dehydrated filtrate of the copper powder slurry are supplied to the replacement leaching step.

次に、図6(b)は塩素浸出液の銅濃度を上昇させる場合のフローシートで、この場合は、従来法に係る金属ニッケルが充填されたカラム槽の充填物を金属銅に置き換えることによって、従来の脱銅電解設備をそのまま利用して、塩素浸出液の銅濃度を上昇させることができる。   Next, FIG. 6B is a flow sheet in the case of increasing the copper concentration of the chlorine leaching solution. In this case, by replacing the packing in the column tank filled with metallic nickel according to the conventional method with metallic copper, Conventional copper removal electrolysis equipment can be used as it is, and the copper concentration of the chlorine leaching solution can be increased.

銅濃度を上昇させた塩素浸出液は、濃度調整工程、銅電解採取工程を通さずに、銅濃度調整液として置換浸出工程に供給される。
本発明は、図6(a)の方法と、図6(b)の方法を組み合わせることにより、塩素浸出液の銅濃度の低下と上昇を自在に切替える。
この方法は、金属ニッケルまたは金属銅を充填した複数のカラム槽と、切替え配管、切替えバルブによって、簡単に実施することができる。
The chlorine leaching solution having an increased copper concentration is supplied to the replacement leaching step as a copper concentration adjusting solution without passing through the concentration adjusting step and the copper electrowinning step.
In the present invention, the reduction and increase of the copper concentration of the chlorine leaching solution can be freely switched by combining the method of FIG. 6 (a) and the method of FIG. 6 (b).
This method can be easily implemented by a plurality of column tanks filled with metallic nickel or metallic copper, switching piping, and switching valves.

以下、実施例を用いて、本発明をより説明する。   Hereinafter, the present invention will be described in more detail with reference to examples.

図7には、塩素浸出によるニッケル製錬プロセスにおいて、本発明によって操業を行った時の、塩素浸出液の銅濃度と混合硫化物の処理比率の推移を示す。この期間は、塩素浸出液の銅濃度の管理基準値を30〜40g/Lに適宜調整して操業を行ったため、混合硫化物の処理比率を50〜55%まで高めることが可能となっている。
図中の「MS原料」は、「混合硫化物(Mixed Sulfide)」を指すものである。
FIG. 7 shows the transition of the copper concentration of the chlorine leaching solution and the treatment ratio of the mixed sulfide when the operation is performed according to the present invention in the nickel smelting process by chlorine leaching. During this period, since the management reference value of the copper concentration of the chlorine leachate was appropriately adjusted to 30 to 40 g / L and the operation was performed, the treatment ratio of the mixed sulfide can be increased to 50 to 55%.
“MS raw material” in the figure refers to “Mixed Sulfide”.

実施例1から、塩素浸出液の銅濃度を調整することにより混合硫化物処理量の処理比率の変化に対応すること、言い換えれば、あらかじめ塩素浸出液の銅濃度を低下させておくことによって、意図的に混合硫化物処理量の処理比率を上昇させることが可能となったことが分かる。   From Example 1, by adjusting the copper concentration of the chlorine leachate, by responding to the change in the treatment ratio of the mixed sulfide treatment amount, in other words, by reducing the copper concentration of the chlorine leachate in advance, It can be seen that the treatment ratio of the mixed sulfide treatment amount can be increased.

実機設備である、容積6m、硬質ゴムが内面にライニングされた圧延鋼製のカラム槽に、100mm×100mm×18mmのサイズに切断した金属銅24100kgを装入した。
そのカラム槽に、塩素浸出液を38〜42L/分の流量で通液した操業を、約5日間、継続した。
24100 kg of metal copper cut into a size of 100 mm × 100 mm × 18 mm was charged into a column tank made of rolled steel having a capacity of 6 m 3 and hard rubber lined on the inner surface, which is an actual equipment.
The operation in which the chlorine leachate was passed through the column tank at a flow rate of 38 to 42 L / min was continued for about 5 days.

得られた塩素浸出液の組成は、Ni濃度が202〜249g/L、Cu濃度が21〜28g/Lであり、金属銅と接触させた後の塩素浸出液のCu濃度は26〜35g/Lとなった。
また、塩素浸出液の酸化還元電位は480〜510mV、2価銅比は51〜72%、金属銅と接触させた後の塩素浸出液の酸化還元電位は430〜450mV、2価銅比は14〜27%であった。
The composition of the obtained chlorine leaching solution has a Ni concentration of 202 to 249 g / L, a Cu concentration of 21 to 28 g / L, and the Cu concentration of the chlorine leaching solution after contact with metallic copper is 26 to 35 g / L. It was.
In addition, the redox potential of the chlorine leachate is 480 to 510 mV, the divalent copper ratio is 51 to 72%, the redox potential of the chlorine leachate after contact with metallic copper is 430 to 450 mV, and the divalent copper ratio is 14 to 27. %Met.

実施例2より、本発明の方法によって、塩素浸出液の銅濃度を上昇させることができることが分かる。   From Example 2, it can be seen that the copper concentration of the chlorine leaching solution can be increased by the method of the present invention.

実機設備である、容積6m、硬質ゴムが内面にライニングされた圧延鋼製のカラム槽に、充填量が20〜24tになるように、100mm×100mm×15mmのサイズに切断した金属ニッケルを約1日毎に追い足し装入した。
そのカラム槽に、塩素浸出液を140〜180L/分の流量で通液した操業を、約7日間、継続した。
About the nickel metal cut to a size of 100 mm x 100 mm x 15 mm so that the filling amount is 20 to 24 t in the column tank made of rolled steel with a volume of 6 m 3 and hard rubber lined on the inner surface, which is an actual equipment. Added and loaded every day.
The operation in which the chlorine leachate was passed through the column tank at a flow rate of 140 to 180 L / min was continued for about 7 days.

1槽当たりアノードが24枚、カソードが23枚載置された脱銅電解槽を8槽用いて、12000A/槽の通電電流にて、約7日間の銅電解採取操業を実施した。
その際、金属ニッケルが充填されたカラム槽に通液した後の塩素浸出液を、Cu濃度が15〜25g/Lになるようにニッケル電解廃液で希釈して、銅電解給液を調製して用いた。
その銅電解給液量は18〜22L/分・槽で、その銅電解給液の組成は、Ni濃度が159〜200g/L、Cu濃度が18〜25g/Lであり、銅電解廃液のCu濃度は10〜14g/Lであった。
The copper electrowinning operation was carried out for about 7 days at an energization current of 12000 A / tank using 8 copper removing electrolyzers on which 24 anodes and 23 cathodes were placed per tank.
At that time, the chlorine leaching solution after passing through the column tank filled with metallic nickel is diluted with a nickel electrolytic waste solution so that the Cu concentration becomes 15 to 25 g / L to prepare a copper electrolytic supply solution. It was.
The amount of copper electrolytic solution supplied is 18 to 22 L / min / tank, and the composition of the copper electrolytic solution is 159 to 200 g / L in Ni concentration and 18 to 25 g / L in Cu concentration. The concentration was 10-14 g / L.

実施例3より、本発明の方法によって、塩素浸出液の銅濃度を低下させることができることが分かる。   From Example 3, it can be seen that the copper concentration of the chlorine leaching solution can be reduced by the method of the present invention.

Claims (2)

ニッケルを含む金属硫化物、又は前記ニッケルを含む金属硫化物と下記セメンテーション残渣を塩素浸出用ニッケル原料として用い、前記塩素浸出用ニッケル原料に含まれるニッケル及び不純物を塩化物水溶液中に塩素浸出して塩素浸出液を得る塩素浸出工程、
前記塩素浸出工程により得られる塩素浸出液に含まれる銅の濃度を、管理基準値(A)に基づいて前記塩素浸出液中の銅濃度を調整した塩素浸出液を得る銅濃度調整工程、
ニッケルを含む金属硫化物に前記塩素浸出液を接触させることで塩素浸出液中の2価銅イオンにより前記ニッケルを含む金属硫化物中のニッケルを置換浸出すると共にCuS又Cuメタルを生成させて銅が除去された置換浸出終液とCuS又はCuメタルを含むセメンテーション残渣を得る置換浸出工程、
前記置換浸出終液中の不純物を除去して塩化ニッケル溶液を得る浄液工程、
前記塩化ニッケル溶液から電解採取法によって金属ニッケルと塩素ガスを回収する電解工程、
を含むニッケルを製造する湿式製錬プロセスにおけるニッケル硫化物原料の処理方法において、
下記(1)から(3)に示す手順に従って、前記塩素浸出液中の銅濃度の管理基準値(A)を低下させることによって、亜硫化ニッケルと金属ニッケルを含むニッケルマットの処理量(B)と、硫化ニッケルと硫化コバルトを含む混合硫化物の処理量(C)との合計原料処理量(B+C)に対する、硫化ニッケルと硫化コバルトを含む混合硫化物処理量(C)の処理比率(D=C÷(B+C)×100%)を上昇させることを特徴とする、ニッケル硫化物原料の処理方法。
(記)
(1)前記ニッケルマットの処理量(B)から許容可能な塩素浸出液中の銅負荷(A1)および塩素浸出液中の銅濃度の上限値(A2)を決定し、
(2)塩素浸出液中の銅濃度の上限値(A2)に対する混合硫化物処理量の処理比率(D)との関係式(D=f(A2))を導き出す。
(3)前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))と、前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))をD軸に沿って−10移動した式(D+10=f(A2+5))と、式A2=15と、式A2=55に囲まれた範囲にある混合硫化物処理量の処理比率(D)に対応した塩素浸出液中の銅濃度の管理基準値(A)を設定する。
Using metal sulfide containing nickel, or metal sulfide containing nickel and the following cementation residue as a nickel raw material for chlorine leaching, leaching the nickel and impurities contained in the nickel raw material for chlorine leaching into an aqueous chloride solution Chlorine leaching process to obtain chlorine leaching solution,
A copper concentration adjusting step of obtaining a chlorine leachate in which the concentration of copper contained in the chlorine leachate obtained by the chlorine leach step is adjusted based on the control standard value (A), the copper concentration in the chlorine leachate,
By bringing the chlorine leaching solution into contact with a metal sulfide containing nickel, nickel in the metal sulfide containing nickel is replaced and leached by divalent copper ions in the chlorine leaching solution, and Cu 2 S or Cu metal is generated to form copper. A substitution leaching step for obtaining a cementation residue containing a substitution leaching final solution from which Cu is removed and Cu 2 S or Cu metal;
A purification step of obtaining a nickel chloride solution by removing impurities in the substitution leaching final solution,
An electrolysis step of recovering metallic nickel and chlorine gas from the nickel chloride solution by electrowinning,
In a method for treating nickel sulfide raw material in a hydrometallurgical process for producing nickel containing,
According to the procedure shown in the following (1) to (3), by reducing the control standard value (A) of the copper concentration in the chlorine leachate, the treatment amount (B) of nickel matte containing nickel subsulfide and metallic nickel The treatment ratio of mixed sulfide treatment amount (C) containing nickel sulfide and cobalt sulfide to the total raw material treatment amount (B + C) of the mixed sulfide treatment amount (C) containing nickel sulfide and cobalt sulfide (D = C) ÷ (B + C) × 100%) is raised, a method for treating a nickel sulfide raw material.
(Record)
(1) Determine the allowable copper load (A1) in the chlorine leachate and the upper limit (A2) of the copper concentration in the chlorine leachate from the nickel mat throughput (B),
(2) A relational expression (D = f (A2)) with the treatment ratio (D) of the mixed sulfide treatment amount with respect to the upper limit (A2) of the copper concentration in the chlorine leachate is derived.
(3) The relational expression (D = f (A2)) is moved by -5 along the A2 axis (D = f (A2 + 5)) and the relational expression (D = f (A2)) is taken as the A2 axis. The equation (D = f (A2 + 5)) moved by -5 along the D axis is surrounded by the equation (D + 10 = f (A2 + 5)) moved by -10 along the D axis, the equation A2 = 15, and the equation A2 = 55. A management reference value (A) for the copper concentration in the chlorine leachate corresponding to the treatment ratio (D) of the mixed sulfide treatment amount in the range is set.
ニッケルを含む金属硫化物、又は前記ニッケルを含む金属硫化物と下記セメンテーション残渣を塩素浸出用ニッケル原料として用い、前記塩素浸出用ニッケル原料に含まれるニッケル及び不純物を塩化物水溶液中に塩素浸出して塩素浸出液を得る塩素浸出工程、
前記塩素浸出工程により得られる塩素浸出液に含まれる銅の濃度を、管理基準値(A)に基づいて前記塩素浸出液中の銅濃度を調整した塩素浸出液を得る銅濃度調整工程、
ニッケルを含む金属硫化物に前記塩素浸出液を接触させることで塩素浸出液中の2価銅イオンにより前記ニッケルを含む金属硫化物中のニッケルを置換浸出すると共にCuS又はCuメタルを生成させて銅が除去された置換浸出終液とCuS又はCuメタルを含むセメンテーション残渣を得る置換浸出工程、
前記置換浸出終液中の不純物を除去して塩化ニッケル溶液を得る浄液工程、
前記塩化ニッケル溶液から電解採取法によって金属ニッケルと塩素ガスを回収する電解工程、
を含むニッケルを製造する湿式製錬プロセスにおけるニッケル硫化物原料の処理方法において、
下記(1)から(3)に示す手順に従って、前記塩素浸出液中の銅濃度の管理基準値(A)を低下させることによって、亜硫化ニッケルと金属ニッケルを含むニッケルマットの処理量(B)と、硫化ニッケルと硫化コバルトを含む混合硫化物の処理量(C)との合計原料処理量(B+C)に対する、硫化ニッケルと硫化コバルトを含む混合硫化物処理量(C)の処理比率(D=C÷(B+C)×100%)を上昇させることを特徴とし、
(記)
(1)前記ニッケルマットの処理量(B)から許容可能な塩素浸出液中の銅負荷(A1)および塩素浸出液中の銅濃度の上限値(A2)を決定し、
(2)塩素浸出液中の銅濃度の上限値(A2)に対する混合硫化物処理量の処理比率(D)との関係式(D=f(A2))を導き出す。
(3)前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))と、前記関係式(D=f(A2))をA2軸に沿って−5移動した式(D=f(A2+5))をD軸に沿って−10移動した式(D+10=f(A2+5))と、式A2=15と、式A2=55に囲まれた範囲にある混合硫化物処理量の処理比率(D)に対応した塩素浸出液中の銅濃度の管理基準値(A)を設定する。
前記銅濃度調整工程は、
前記塩素浸出液の銅濃度が、15〜55g/Lの間で任意に設定された管理基準値(A)から3g/L以上低下した時には、下記(イ)、(ハ)のいずれかの手順を講じ、
前記塩素浸出液の銅濃度が、前記管理基準値(A)から3g/L以上上昇した時には、下記(ロ)の手段を講じ、
前記塩素浸出液の銅濃度が、前記管理基準値(A)から3g/L未満低下した時には、下記(イ)、(ロ)、(ハ)のいずれかの手段を講じ、
前記塩素浸出液の銅濃度が、前記管理基準値(A)から3g/L未満上昇した時には、下記(イ)、(ロ)、(ハ)のいずれかの手段を講じて、
塩素浸出液中の銅濃度を10g/L以上60g/L以下の範囲に維持することを特徴とする、ニッケル硫化物原料の処理方法。
(記)
(イ)酸化還元電位が400mV(Ag/AgCl電極基準)以上の塩素浸出液と金属銅を接触させることによって、塩素浸出液中の銅濃度を上昇させる銅補充手段。
(ロ)塩素浸出液を還元して価数が2価の銅イオン濃度を低下させた後に、前記還元後の塩素浸出液を銅電解採取することによって、塩素浸出液中の銅濃度を低下させる脱銅手段。
(ハ)上記(イ)も(ロ)も実施しない中立手段。
Using metal sulfide containing nickel, or metal sulfide containing nickel and the following cementation residue as a nickel raw material for chlorine leaching, leaching the nickel and impurities contained in the nickel raw material for chlorine leaching into an aqueous chloride solution Chlorine leaching process to obtain chlorine leaching solution,
A copper concentration adjusting step of obtaining a chlorine leachate in which the concentration of copper contained in the chlorine leachate obtained by the chlorine leach step is adjusted based on the control standard value (A), the copper concentration in the chlorine leachate,
By bringing the chlorine leaching solution into contact with a metal sulfide containing nickel, nickel in the metal sulfide containing nickel is substituted and leached with divalent copper ions in the chlorine leaching solution, and Cu 2 S or Cu metal is generated to form copper. A substitution leaching step for obtaining a cementation residue containing a substitution leaching final solution from which Cu is removed and Cu 2 S or Cu metal;
A purification step of obtaining a nickel chloride solution by removing impurities in the substitution leaching final solution,
An electrolysis step of recovering metallic nickel and chlorine gas from the nickel chloride solution by electrowinning,
In a method for treating nickel sulfide raw material in a hydrometallurgical process for producing nickel containing,
According to the procedure shown in the following (1) to (3), by reducing the control standard value (A) of the copper concentration in the chlorine leachate, the treatment amount (B) of nickel matte containing nickel subsulfide and metallic nickel The treatment ratio of mixed sulfide treatment amount (C) containing nickel sulfide and cobalt sulfide to the total raw material treatment amount (B + C) of the mixed sulfide treatment amount (C) containing nickel sulfide and cobalt sulfide (D = C) ÷ (B + C) x 100%),
(Record)
(1) Determine the allowable copper load (A1) in the chlorine leachate and the upper limit (A2) of the copper concentration in the chlorine leachate from the nickel mat throughput (B),
(2) A relational expression (D = f (A2)) with the treatment ratio (D) of the mixed sulfide treatment amount with respect to the upper limit (A2) of the copper concentration in the chlorine leachate is derived.
(3) The relational expression (D = f (A2)) is moved by -5 along the A2 axis (D = f (A2 + 5)) and the relational expression (D = f (A2)) is taken as the A2 axis. The equation (D = f (A2 + 5)) moved by -5 along the D axis is surrounded by the equation (D + 10 = f (A2 + 5)) moved by -10 along the D axis, the equation A2 = 15, and the equation A2 = 55. A management reference value (A) for the copper concentration in the chlorine leachate corresponding to the treatment ratio (D) of the mixed sulfide treatment amount in the range is set.
The copper concentration adjusting step
When the copper concentration of the chlorine leachate is reduced by 3 g / L or more from the control reference value (A) arbitrarily set between 15 and 55 g / L, the procedure of either (a) or (c) below is performed. Take,
When the copper concentration of the chlorine leachate is increased by 3 g / L or more from the control reference value (A), the following measures (b) are taken,
When the copper concentration of the chlorine leachate is reduced by less than 3 g / L from the control standard value (A), the following measures (a), (b), (c) are taken,
When the copper concentration of the chlorine leachate is increased by less than 3 g / L from the management reference value (A), take one of the following means (a), (b), (c)
A method for treating a nickel sulfide raw material, characterized in that a copper concentration in a chlorine leachate is maintained in a range of 10 g / L to 60 g / L.
(Record)
(A) Copper supplementation means for increasing the copper concentration in the chlorine leachate by bringing the copper leachate having a redox potential of 400 mV (Ag / AgCl electrode standard) or more into contact with metallic copper.
(B) Decoppering means for reducing the copper concentration in the chlorine leaching solution by reducing the chlorine leaching solution to reduce the copper ion concentration having a valence of 2 and then collecting the leached chlorine leaching solution by copper electrolysis. .
(C) Neutral means that does not implement (i) or (b) above.
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